RU2051141C1 - Steric hindered phenols having antioxidant properties, methods for their production, method for production of polyolefins - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: desired steric hindered phenols have formula I where R₁ and R₂ are substituents as mentioned below, R₃ is hydrogen atom or lower alkyl, n=0-3 or A is (R₁R₂) where R₁ and R₂ are steric hindered substituents; R₁ having formula II and R₂ is identical to R₁ or it has formula III. In these formulae X and X′ are the same or different and represent oxygen atom, each of R₄, R₅, R₆, R₇ is C₁-C₈-alkyl or R₄ and R₆ may be additionally hydrogen atom and R₈ is hydrogen, methyl or ethyl. Antioxidants are prepared by interaction of bisubstituted phenol and appropriate β- or g-unsubstituted norbornenon in alcohol medium with the help of basic catalysis. Proposed phenol antioxidants are used for production of polyolefins, the process is carried out by polymerization of a-olefins or by their copolymerization and/or by copolymerization with dienes, mass ratio phenol antioxidant and monomer being 0.1:(40-100). (Co)polymerization is carried out till content of phenol said phenol oxidant being bound with said (co)polymer is 0.05-20 mass per 100 mass of (co)polymer. Structures of compounds having formulae II and III are given in specification. EFFECT: improves quality of desired product, improves efficiency of method. 9 cl, 1 dwg, 13 tbl

Description

 The invention relates to antioxidants that can be polymerized with other monomers in the form of copolymers, giving the polymers antioxidant properties, and to oxidizing agents and methods for their preparation for use in the creation of such polymers.

 The invention relates to polyolefins having antioxidant properties and prepared by Ziegler polymerization of a polymerizable monomeric antioxidant with alpha olefins. In addition, this invention provides a method for introducing functional bonds into polyolefins by Ziegler catalysis without undue use of co-catalysts or passivating agents. The development of the well-known Ziegler catalyst system made it possible to polymerize alpha-olefins to commonly used polymers and copolymers.

 One of the fundamental drawbacks of the Ziegler catalyst system is that it cannot be used for monomers containing functional groups that are polar in nature. As a rule, such polar functional groups tend to irreversibly react with the components of the Ziegler catalyst system, thus reducing the actual concentration of these components.

 It is also well known that virtually all polyolefins require stabilization to avoid uncontrolled oxidation, which tends to cause unwanted changes in the polymer, including chain degradation, crosslinking and discoloration, and thus adversely alters the mechanical and physical properties of the polymer. In the field of stabilization, large-scale studies have been undertaken, the result of which was the creation of a number of antioxidants that give polyolefins, including highly elastic polyolefins, greater stability. The main class of antioxidants that have been developed over the years is the class of hindered phenols.

 Although molecular antioxidants such as hindered phenols have become widely used in the stabilization of a significant amount of polyolefins, they tend to migrate from the polymer under certain conditions, which leads to depletion of the antioxidant in the polymer and, therefore, the polymer tends to decompose upon oxidation. The use of bound antioxidants that remain in the polymer under conditions conducive to the migration of molecular polymers is justified in the following sources: (1) Klein R.Kh. and Miller, J.P. Preparation and Effect of Polymerizable Antioxidants for Emulsified Rubbers. Chemistry and Rubber Technology, 46.96 (1973); (2) Meyer, G.E. Kavchok, R.V. and Napples F.J. Emulsified rubbers copolymerized with monomeric antioxidants. Chemistry and Technology of Rubbers, 46.106 (1973); (3) Horvath J.V. Associated NBR Stabilizing Antioxidant. Application in the automotive industry. Elastic Polymers, August 1979, p. 19; (4) Kutzkowski, J.A. and Gillick, J., Polymer-Bound Antioxidants. Chemistry and Technology of Rubbers, 57, 621 (1984); (5) Engels H.V. and others. The effectiveness of new alkyl-acryl-p-phenylenediamines, which can be associated with polymers chemically. Study of the model. Chemistry and Technology of Rubbers, 62, 609 (1989); (6) Parker D.K. and Schulz G.O. Polymerizable amine antioxidant N- (4-anilinophenyl) methacrylamide. Synthesis, copolymerization, copolymer properties and characteristics. Chemistry and Technology of Rubbers, 62, 732 (1989); (7) Gandek, T.P. Hatton, T.A. and Reid R.K. Single extraction and reaction: migration of a phenolic antioxidant from polyolefins to water. Results and discussion of the experiment. Independent Journal of Chemical Engineering Engineering. 28, 1036 (1989); (8) Miller D.E. and other Persistent antioxidants for polymers in contact with extractive media. World of rubbers, August 1989, p. 13. Such antioxidants are characterized as polymer-bonded for the reason that they are chemically bonded to the polymer either by the grafting reaction or by copolymerizing with olefin monomers during the preparation of the polymer itself.

 The polymer-bound antioxidants resulting from copolymerization with other monomers are limited to free radical polymerizations, in particular to copolymerization of butadiene and acrylonitrile free radical emulsions in the production of butadiene-acrylonitrile rubbers. Common monomers of polymer-linked antioxidants include an amide or derivatives of acrylic or methacrylic acid esters, which can be copolymerized by the formation of free radicals with butadiene and acrylonitrile. Although such polymer-bound antioxidants are suitable as monomers for free radical polymerization technologies, they are not suitable for use in Ziegler catalyst-catalyzed polymerizations because their polar groups tend to act as substances that reduce the activity of the catalyst.

где R₁ либо R, либо OR, а R алкил, акрил или циклоалкил, содержащий 1-18 атомов углерода или водорода.In US patents N 3748316, 3796687 and 4017669 proposed to carry out the copolymerization of polar monomers using a Ziegler catalyst. Characteristically, in these earlier patents certain norbenene compounds having a phenolic group are chemically bonded by copolymerization with ethylene and propylene on a Ziegler catalyst. General principles used in referenced patents include said compound having the following general formula

where R _{1 is} either R or OR, and R is alkyl, acrylic or cycloalkyl containing 1-18 carbon or hydrogen atoms.

 These three patents do not describe such methods by which compounds of this type can be obtained, and do not describe the polymerization with such a monomer. Therefore, these patents do not provide information about such compounds and polymers derived from them. In addition, it is important to note that in these patents it is proposed to overcome the poisoning of the catalyst by polar groups by using, together with the polar monomer (this is not the monomer discussed above), an equal amount of a molar aluminum alkyl solution, a solution very expensive, as well as very impractical with environmental and safety aspects used in the modern rubber and plastics industry. Moreover, the idea of the possibility of a phenolic-type polar monomer to impart antioxidant properties to the polar copolymer obtained by the methods described in these patents is not given.

как имеющие реактивную двойную связь и тем самым являющиеся полимеризуемыми.US Pat. No. 4,301,306 describes norbornenyl monophenol compounds with the general formula

as having a reactive double bond and thereby being polymerizable.

 However, this patent does not indicate how to use the reactive norbornenyl phenolic compound in polymerization reactions, nor how to demonstrate that, after polymerization, the copolymer thus obtained has antioxidant properties.

 The norbornenyl monophenol compounds described above were the subject of invention in US Pat. like 1-hexene.

 The purpose of the invention is to provide polymerizable antioxidants and methods for their preparation, wherein the polymerizable antioxidant can be copolymerized with another monomer or mixture of monomers to impart antioxidant properties to the resulting copolymer.

 The narrower objective of this invention is to provide polymerizable antioxidant compounds that can be prepared by simple and inexpensive methods and which can be copolymerized with other polymerizable monomers by any of the well-known Ziegler methods without catalysis poisoning.

 In accordance with the foregoing, another objective of the present invention is to obtain polyolefins having antioxidant properties and prepared by conventional Ziegler polymerization processes in which an olefin-containing antioxidant is copolymerized with an alpha-olefin or a mixture of olefins and embedded directly in the main polymer chain.

 Another objective of the present invention is to introduce functional bonds into polyolefins directly by Ziegler catalysis and without the use of special technologies such as the use of passivating groups and the costly use of an organoaluminum catalyst with joint effects.

 The principles underlying this invention are the use of Ziegler polymerizable antioxidant compounds in the form of norbornene with substituted atoms, in which the substituent contains alkyl groups that confer antioxidant properties to the compound. Among the substituents imparting antioxidant properties, the preferred are hydroxy-substituted aromatic groups, and the most preferred are alkyl-substituted phenols.

(I) в которой n 0-3, R₁ ариловый радикал, придающий антиокислительные свойства; R₂ либо атом водорода, либо ариловый радикал, придающий антиокислительные свойства; R₃ либо атом водорода, либо алкиловая группа:
или соединения, имеющие формулу

где R₁ и R₂ каждый являются ариловым радикалом, придающим антиокислительные свойства.In accordance with this invention, Ziegler polymerizable antioxidants are compounds having the general formula

(I) in which n is 0-3, R _{1 is an} aryl radical imparting antioxidant properties; R _{2 is} either a hydrogen atom or an aryl radical imparting antioxidant properties; R _{3 is} either a hydrogen atom or an alkyl group:
or compounds having the formula

where R ₁ and R ₂ are each an aryl radical conferring antioxidant properties.

(II) а R₂ имеет формулу
R

(III)
В каждой из этих формул Х и Х¹ выбираются из двухвалентного атома кислорода и двухвалентного атома серы; R₄, R₅, R₆ и R₇ каждый в отдельности являются независимыми алкилами, содержащими 1-8 атомов углерода, такими как метил, этил, изопропил, бутил, трет-бутил, пентил, изопентил и т.д. или, помимо этого, R₄ и R₅ могут быть водородом, R₈ водородом или метилом, или этилом, или смесью названных веществ, а R₃ в упомянутой выше формуле либо водород, либо такой алкил, как метил, этил, пропил и т.д.In a preferred embodiment, R ₁ has the formula
R

(II) and R ₂ has the formula
R

(III)
In each of these formulas, X and X ¹ are selected from a divalent oxygen atom and a divalent sulfur atom; R ₄ , R ₅ , R ₆ and R ₇ are individually independent alkyls containing 1-8 carbon atoms, such as methyl, ethyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl, etc. or, in addition, R ₄ and R ₅ may be hydrogen, R _{8 is} hydrogen or methyl, or ethyl, or a mixture of these substances, and R ₃ in the above formula is either hydrogen or an alkyl such as methyl, ethyl, propyl, etc. .d.

 A suitable monophenol olefin for the synthesis, containing an antioxidant and corresponding to this invention, is disclosed in US patent N 4301306 (author Leyer), and in this description is given for reference. Layer uses the well-known Diels-Adler reaction to form 2-norbornene substituted at the 5th position with an alkylene or alkylene phenol group by reacting cyclopentidien with 4-alkenyl phenol as shown below.

Особо предпочтительные примеры реализации данного изобретения должны включать следующие структуры

Cреди упоминавшихся выше бисфенолонорборненов предпочтительными являются соединения, показанные на чертеже.

Particularly preferred embodiments of the present invention should include the following structures

Among the bisphenolonorbornenes mentioned above, the compounds shown in the drawing are preferred.

К подходящим 2-норборнен-карбоксильным соединениям следует отнести те, в которых R₃-водород или такая алкиловая группа, как метил, этил, пропил и т. д. с карбоксильным замещением в любом из положений норборненового кольца, за исключением атомов углерода с двойными связями.The bisphenol polymerizable antioxidants of the invention can be prepared based on a catalyzed condensation reaction of a disubstituted phenol and / or a disubstituted thiophenol with a 2-norbornene-carboxyl compound according to the following equation

Suitable 2-norbornene-carboxyl compounds include those in which the R _{3 is} hydrogen or an alkyl group such as methyl, ethyl, propyl, etc. with a carboxyl substitution at any position of the norbornene ring, with the exception of carbon atoms with double connections.

тоже должны подойти в качестве исходных материалов для реакции конденсации с фенолами или тиофенолами, дающей полимеризуемые антиокислители следующих структур

Подходящие для применение данного изобретения на практике двузамещенные фенолы и/или двузамещенные тиофенолы должны иметь в качестве каждой из групп R₄ и R₅ такой независимый алкил, содержащий 1-8 атомов углерода, как метил, этил пропил, изопропил, бутил, трет-бутил, пентил, изопентил и т.д.Beta, gamma-unsaturated norbornenones of the type shown below

should also be suitable as starting materials for the condensation reaction with phenols or thiophenols, giving polymerizable antioxidants of the following structures

Suitable for the practice of this invention, disubstituted phenols and / or disubstituted thiophenols must have, as each of the groups R ₄ and R _5, such independent alkyl containing 1-8 carbon atoms as methyl, ethyl propyl, isopropyl, butyl, tert-butyl pentyl, isopentyl, etc.

В случае, когда две фенольные и/или тиофенольные группы замещаются на одну и ту же молекулу норборнена, соответствующий полимеризуемый антиокислитель может быть приготовлен путем использования подходящей смеси, обычно эквимолярной смеси двух фенолов, тиофенолов или смеси фенола с тиофенолом, чтобы сформировать должным образом перемешанный продукт.A representative reaction product between 2-norbornene-5-carboxyaldehyde and two equivalents of 2,6-di-tert-butylphenol was called bisphenol-N and is depicted as follows

In the case where two phenolic and / or thiophenol groups are replaced by the same norbornene molecule, the corresponding polymerizable antioxidant can be prepared by using a suitable mixture, usually an equimolar mixture of two phenols, thiophenols or a mixture of phenol and thiophenol, to form a properly mixed product .

 The reaction can be carried out by dissolving phenol or thiophenol in a solvent such as a lower alcohol such as methyl alcohol, and then adding potassium hydroxide in the dissolved state. Then 2-norbornene-5-carboxyaldehyde is added, followed by neutralization and isolation of the target compound or mixture of compounds.

 The use of a mixture of phenol, a mixture of thiophenols or a mixture of phenol and thiophenol will be appreciated by those skilled in the art, since the reaction product will then be a mixture of compounds in which the norbornene molecule is replaced by mixed phenols and thiophenols.

 The Ziegler polymerizable antioxidants of the invention generally find particular use as copolymers in the Ziegler catalyzed olefin polymerization reaction. Thus, the antioxidant according to the present invention can copolymerize with alpha olefins such as ethylene, propylene, butene or hexene, with or without conjugated double bonds such as butadiene, isoprene and 1,4-hexadiene, and with styrene. In addition, the antioxidants corresponding to the present invention can be used as copolymers in the polymerization reaction of olefin mixtures in the preparation of trimers, tetramers, etc. The resulting polymers containing antioxidants can be crystalline or amorphous and are widely used from plastics to elastomers.

Typical Ziegler catalysts used in the practice of this invention consist of a transition metal compound, the metal being selected from Groups IV-VI of the Table of the Periodic Table of the Elements (as published in the Chemical and Physics Catalog by Ze Chemicalel Rber Company, Cleveland, pc. Ohio, USA) and is used in combination with an alkylate or hydride of a base metal, with at least one group having a bond of a carbon atom with a metal, the metal being selected from groups I-III of the Table of the Periodic Table of the Elements. Examples of commonly used transition metals should include vanadium, titanium, zirconium, cobalt, chromium and nickel. Examples of commonly used basic metal alkylates are various organoaluminum compounds, organoaluminum halides, organozinc compounds or organomagnesium compounds. Transition metal compounds may be homogeneous or heterogeneous and may be in complex or in combination with electron-donating chemicals such as organic esters, amines, phosphines, silicates and other substances. Alternatively, the transition metal may be supported on an inert support such as MgO, MgCl ₂ , silica or alumina. For the practice of the present invention, in particular for the preparation of bound polyethylenes with an antioxidant, it is acceptable when CrO _{3 is} supported on an activated aluminosilicate, that is, a catalyst, also known as a Phillips catalyst.

 The Ziegler polymerization reaction with a monomeric olefin containing an antioxidant is not limited by the process conditions and can be carried out in solution, suspension, gas phase, or in any combination of such processes. As is known to those skilled in the art, the choice of process will depend on the type of polyolefin and the specific Ziegler catalyst system.

 The active Ziegler catalyst does not experience negative effects from the monomer of the polymerizable antioxidant. You can use standard Ziegler polymerization methods, including molecular weight control methods well known to those skilled in the art, to produce polymers with bound antioxidant at the same molecular weight, molecular weight distribution, the same stereospecificity, and the same comonomer levels as for standard polymers. The molar ratio of the components of the base metal alkylate catalyst to the transition metal component does not change. No step is required to add catalyst components. A preliminary reaction of the base metal alkyl with the monomer of the polymerizable antioxidant is neither required nor desirable.

 A useful example of the Ziegler polymerization of the antioxidant of this invention with a mixture of alpha olefins is the preparation of ethylene-propylene copolymer rubbers and the trimerization of polyethylene, alpha-olefin with 3-18 carbon atoms and a diene without conjugated double bonds as in the preparation of ethylene-propylene triple -diene copolymer rubbers. Dienes suitable for the preparation of such ethylene-propylene-diene copolymer terpolymers include 1,4-hexadiene, monocyclic polyenes and polycyclic polyenes. Representatives of such compounds are dichloropentadiene, octadiene, cyclo- (2,2,1) -hepta-2,5-diene, alkyl diene norbornenes in which the alkyl diene group contains from one to twenty carbon atoms and preferably from one to eight carbon atoms, olefinic norbornenes and, in particular, 5-alkenyl-2-norbornenes in which the alkenyl group contains from three to twenty carbon atoms. Other suitable polyenes having rings with internal bridges are polyunsaturated derivatives of bicyclo- (2,2,2) -hexane, such as bicyclo- (3,2,1) -hexane, polyunsaturated derivatives of bicyclo- (3,3,1) nonane and polyunsaturated derivatives of bicyclo- (3,3,1) nonane and polyunsaturated derivatives of bicyclo- (3,2,2) nonane.

 Examples of preferred compounds having rings with internal bridges are 5-methylene-2, norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-n-propylidene-2-norbornene, 5-isobutylidene 2-norbornene, 5-n-butylidene-2-norbornene, dicyclopentadiene, 5- (2-methyl-2-butenyl) -2-norbornene, 5- (3-methyl-2-butenyl) -2-norbornene and 5- (3,5-dimethyl-2-hexenyl) -2-norbornene.

 The copolymer ethylene-propylene / ethylene-propylene-diene rubbers containing the polymerizable antioxidants of the invention and incorporated into the main polymer chains have a molar ratio of ethylene to propylene (or another monoolefin containing 3-16 carbon atoms), varying from 95: 1 to 5 : 90 (ethylene: propylene) and preferably from 85:15 to 55:45. Polyene or substituted polyene is chemically bonded in triple ethylene-propylene-diene rubber, and its amount is 0-30% by weight. The monomeric polymerizable antioxidant according to the invention is bound in the backbone of the polyolefin in an amount of 0.001-20% by weight, which depends, in particular, on the particular use of the polymer. The same amount of polymerizable antioxidant can be used in the other polymers described above.

 Such polymers are produced by copolymerization in the presence of a Ziegler catalyst well known to those skilled in the art. Methods for producing such ethylene-propylene or ethylene-propylene-diene copolymers are well known and are described in US Pat. Nos. 2,933,480, 3,093,621, 3,211,709, 3,645,168, 3,790,519, 3,884,993, 3,894,999 and 4,059,654, as well as in many other patents.

 The monomers of the polymerizable antioxidant described here are usually applicable for copolymerization with ethylene to create high density polyethylene, including ultrahigh molecular weight polyethylene, and ethylene and such alpha olefins as butylene, hexane and octene, to obtain polyethylene with a low linear density. The reaction is carried out according to standard conditions, which are well known to specialists in this field of technology, when the monomer of the polymerizable antioxidant is added in the form of a solution of hexane, toluene, in the form of a liquid monomer or alkene hydrocarbons.

 The copolymerization of the monomers of the polymerizable antioxidant according to the invention with propylene or with mixtures of propylene and alpha-olefins at a level of 0.01-1.0% by weight gives thermoplastic propylene polymers that are resistant to self-oxidation and thus suitable for processing under less stringent conditions its compared to conventional polypropylenes such as thermoplastics.

 Thus, the polymerizable antioxidant of the present invention is copolymerized with alpha olefin or mixtures of alpha olefins and serves to impart antioxidant properties to the polymer. One of the advantages of this invention is that, unlike antioxidants that are physically miscible with the polymer composition and tend to migrate through the polymer matrix, the polymerizable antioxidants of this invention are not susceptible to such migration because they are chemically bonded to the polymer matrix. The implementation of the present invention also overcomes the tendency to release or leach the antioxidant from the formed polymer product when contact with the liquid remains until the end of the reaction. The incorporation into the backbone of a polyolefin of a polymerizable antioxidant in an amount of 0.1-2.0% by weight is manifested in oxidation stability upon receipt, transportation and storage. The incorporation into the backbone of a polyolefin of a polymerizable antioxidant in an amount of 0.5-20% by weight provides oxidation resistance for high temperature processing of the polyolefin. At such high levels of copolymerized antioxidant, the polyolefin will also be suitable for mixing with polyolefins and / or polymers that do not have antioxidant properties.

 Consider the following examples, which are provided for illustration and not limitation, and which discusses possible ways of practical implementation of the present invention in the preparation of the polymerizable antioxidants of this invention and in their use in the copolymerization reaction with various monomers.

 Example 1. Preparation and characterization of the condensation product of 2,6-di-tert-butylphenol with 2-norbornene-5-carboxyaldehyde, which is called bis-phenol N (BFN).

 Synthesis of bisphenol.

The reaction is carried out in a flask with three necks, having a capacity of 500 ml and equipped with a mechanical stirrer, an additional funnel, a refrigerator and indirect heating. The flask was charged with methanol reagent containing 5.2 g of diluted KOH, which is 0.08 mol of KOH. After this, 41.2 g (0.2 mol) of 2,6-di-tert-butylphenol are added. The mixture is placed under nitrogen, carefully loaded and stirred until phenol dissolves. A solution of 9.8 g (0.08 mol) of 5-norbornene-2-carboxyaldehyde (mixture of isomers) in 20 ml of methanol is added dropwise through an additional funnel, stirring. The reagent mixture is heated at reflux for 16 hours, after which it is allowed to cool to room temperature. A precipitate forms, which can be collected by filtration and washed with fresh methanol. The product was a white powder having a melting temperature of 203-205 ^C. The product yield turns in an amount of 20.0 g corresponding to 48% of the theoretical yield.

Characterization of bisphenol
Bisphenol N is a colorless crystalline solid having a melting point of 204-205 ^C. The IR spectrum of Bisphenol N detects the absorption bands are listed in the Table. 1.

 Peaks-mass spectra (study of solid particles, 70 eV) are listed in table. 2.

The proton and nuclear ( ¹³ C) magnetic resonance spectra of bisphenol N are consistent with the interpreted structure. Nuclear magnetic resonance (NMR) data show that BFN is a mixture of exo and endo isomers. This is confirmed by liquid phase chromatography.

Elementary analysis:
Calculated for C ₃₆ H ₅₂ O ₂ : C 83.65; H 10.16; About 6.19.

 Found (according to the results of the calculation of the experiment): C 83.85, H 10.16, O 5.99.

 PRI me R 2. The copolymerization of bisphenol N with ethylene and propylene.

During a typical polymerization in this case, a 2.0 ml solution of 4.09 g of recrystallized bisphenol N in 8.61 g of toluene is added to a Sutherland dispenser containing 3.8 mmol of ethyl aluminum sesquichloride, 0.4 mmol of vanadyl chloride, 0.3 mmol of pyridine and 0.05 mmol of butyl perchlorovinyl acetate in 900 ml of hexane, and copolymerized with ethylene and propylene. The temperature in the dispenser was 38 ^{° C} and the total pressure of 0.3 MPa. The pressure in the dispenser is maintained throughout the entire operating time by adding a mixture of 60% ethylene and 40% propylene. 20 minutes after the start, the reaction was stopped by suppressing the catalyst with 1.0 g of isopropyl alcohol, and the obtained polymer (19.0 g) was precipitated by adding the reacted mixture to isopropyl alcohol.

The polymer obtained in Example 2 was isolated using cyclohexane in acetone to remove any residual monomer, and then checked by infrared spectroscopy. The presence of bisphenol N is indicated by a hydroxyl absorption band at a frequency of 3610 cm ^-1 .

 PRI me R 3. Generalized procedure used for the copolymerization of ethylene, propylene and ethylidene norbornene.

 150 g of hexane, 0.8 mmol of ethyl aluminum sesquichloride, 0.065 mmol of vanadyl chloride, 0.02 mmol of butyl perchlorovinyl acetate, 0.3 g of ethylidene norbornene and 0.05 mmol of pyridine are placed in a corked bottle. During the reaction, a pressure of 0.31 MPa is maintained by adding a mixture that contains 60% ethylene and 40% propylene. The reaction is carried out at room temperature and stopped 20 minutes after the start by adding isopropyl alcohol.

 The following examples illustrate the copolymerization of bisphenol with ethylene, propylene and ethylene norbornene.

 PRI me R s 4-8. The polymerization reaction is carried out as described in example 3, with the addition of various amounts of bisphenol N in a 30% solution of toluene. The weight of the total amount of the reacted mixture is determined after the reaction, and the solution is analyzed for residual bisphenol N by high pressure liquid chromatography. The results of the analysis are summarized in table 3. During chromatographic analysis, it was noted that standard solutions of bisphenol N monomer found two peaks, which could be related to two isomers of bisphenol N. The ratio of these peaks in the starting material ranged from 1.05 to 1.09. The presence of a larger value of the indicated ratio for residual bisphenol N indicates that both isomers polymerize to different degrees.

 The data in Table 3 show that the polymer yield and catalyst life are not negatively affected by an increase in the content of bisphenol N in the polymerized substance. In each of the polymers, 5–7 percent of the chemical conversion of bisphenol N is approximately 90–95, and its behavior is similar to that of ethylidenenorbornene, in which the percentage of copolymerization was independent of concentration.

 PRI me R 9A. The general procedure used for the synthesis of the analog of bisphenol N-alpha, alpha-bis (2,6-dimethylphenol) -5-methylene-2-norbornene.

The reaction is carried out in a round bottom flask with three necks with a capacity of 200 ml, equipped with a refrigerator, a mechanical stirrer and a rubber diaphragm. 50 ml of methanol reagent, 5.2 g (0.08 mol) of KOH in tablets and 24.4 g (0.2 mol) of 2,6-dimethylphenol are charged into the flask. The reaction is carried out in an atmosphere of nitrogen, allowing it to pass through the diaphragm and exit through the refrigerator in the form of bubbles containing mineral oil. 5-Norbornene-2-carboxyaldehyde (9.8 g, 0.08 mol) was added via diaphragm injection. The reaction mixture is heated at reflux for 16 hours with stirring. After cooling, the product remains in solution. The solution was neutralized with four molar HCl to pH 5-7. The mixture was diluted with 100 ml of dichloromethane. Then, three times washing in a separatory funnel in portions of fresh water of 30 ml is carried out. The solution was dried with magnesium sulfate. After filtration to remove the drying agent, the solution was evaporated to obtain 27.5 g of a solid residue. This residue is purified using a chromatographic column (silica gel, 1/1 hexanedichloromethane) and 16.5 g of product are obtained, the yield being 59% of the theoretical value. Recrystallization from toluene provided colorless crystals which have a melting temperature ^of 176-178 C. This product is an analog of Bisphenol N, having a phenol rings in place of tert-butyl groups instead of methyl groups.

 PRI me R 9V. Polymerization of a triple ethylene-propylene-diene copolymer with alpha, alpha bis (2,6-dimethylphenol) -5-methylene-2-norbornene.

 900 ml of dehydrated hexane, purged with nitrogen and propylene to remove traces of oxygen, are charged to the Sutherland dispenser and pressure is raised to 0.17 MPa by compression with propylene. To bring the total pressure in the dispenser to 0.31 MPa, an additional amount of the mixture containing 60% ethylene and 40% propylene is added.

Thereafter, 4.8 mmol of ethyl aluminum sesquichloride, 0.3 mmol of pyridine, 0.15 mmol of butyl perchlorovinyl acetate, 0.192 g of dimethyl analog of bisphenol N added as a solution in toluene, and 0.05 mmol of vanadyl trichloride are added to the dispenser. The reaction temperature is ⁴⁰ ° C, the pressure in the dispenser is maintained at 0.31 MPa throughout the reaction time, pressure is maintained by adding raw material containing 60% of ethylene. The reaction is interrupted 20 minutes after the start by adding 1.0 ml of isopropanol. The polymer is coagulated in isopropanol and dehydrated in a vacuum oven.

 A total of 5.8 g of polymer was obtained. He had a solution viscosity reduced to 2.08. The polymer had 65.1% by weight of ethylene and 0.79% by weight of alpha, alpha bis (2,6-dimethylphenol) -5-methylene-2-norbornene, as determined by IR analysis.

 PRI me R 10. Polymerization of polypropylene with bisphenol N using a titanium catalyst.

500 ml of dehydrated hexane was charged into the Sutherland dispenser and purged with nitrogen and then with propylene to remove traces of oxygen. After the dispenser was added 5.4 mmol of diethylaluminum chloride in hexane, the temperature is increased to 60 ^C. Then, the dispenser is charged with 0.18 g of Bisphenol N in hexane and 2.7 mmole of titanium trichloride catalyst. Using propylene, the pressure in the dispenser immediately increases to 0.31 MPa. It is supported at this level by constant additives of propylene. After 1 h, the reaction was stopped by adding 10 ml of methanol. 24 g of crystalline polypropylene was recovered by filtration after the hexane slurry was extracted twice with 400 ml of water. IR analysis of oven-dried polypropylene showed the presence of bisphenol N in an amount of 0.3% by weight.

 PRI me R s 11 AE. The copolymerization of bisphenol IX with ethylene and propylene.

The polymers are obtained, as in example 3, except that ethylidene norbornene was not used. The presence of bisphenol N in the solution at the end of the polymerization reaction is not observed. The polymers are reduced by coagulation with isopropanol, dehydrated at room temperature in vacuo and used as samples in the analysis based on the absorption band of the infrared spectrum at a frequency of 3610 cm ^-1 . The results are shown in table. 4.

 Example 12 and 13. The following examples 12A-E and 13A-E compare the polymerization of ethylene, propylene and bisphenol N in toluene and ethylidene norbornene as solvents.

 PRI me R 12 A-E. The polymers were prepared according to the method described in Example 2, except that 0.2 mmol of vanadium chloride and 0.1 mmol of butyl perchlorovinyl acetate were used. Bisphenol N is added as a solution of 0.6 g of bisphenol N in 25 ml of toluene. The results are shown in table 5.

 Since bisphenol N is a solid particle at room temperature, it is convenient to add it to the reactor where the polymerization takes place, in the form of a solution in an inert solvent. Although toluene is an excellent solvent for bisphenol N, other solvents may also be used. Generally speaking, any solvent that does not contain polar groups that poison the catalyst can be used. In particular, ethylidene norbornene is an acceptable solvent for introducing bisphenol N into EPDM reactors since it is already added as a comonomer.

 PRI me R s 13 AE. The polymers are obtained by the method described in example 2, except that the addition of bisphenol N is carried out in the form of a solution of 1 g of bisphenol N in 25 ml of ethylidene norbornene. In addition, an additional amount of ethylidene norbornene is added so that its total amount is 1.0 g. The results are shown in Table 6.

 PRI me R 14. A copolymer of polyethylene with bisphenol N obtained using a vanadium catalyst.

900 ml of dehydrated hexane and 0.16 g of bisphenol N are loaded into the Sutherland dispenser, then they are purged several times to get rid of traces of oxygen, and using ethylene, the pressure is increased to 0.28 MPa. To control molecular weight, hydrogen is added at a pressure of 0.03 MPa. The reactor was heated ^to 40 ° C and catalyst components added in the following sequence: 4.8 mmol ethylaluminum sesquichloride, butyl perchlorovinylacetate 0.12 mmol and 0.02 mmol of vanadyl trichloride. Ethylene is added continuously throughout the reaction to maintain a pressure of 0.31 MPa in the dispenser. 20 minutes after the start of the reaction, 1.0 ml of isopropanol was added to stop the reaction. The resulting polymer (7.6 g) was reduced and then diluted twice with trichlorobenzene and reprecipitated before being analyzed by IR spectroscopy for the presence of bound phenolic groups. IR analysis showed that polyethylene contains bisphenol N in an amount of 0.64% by weight.

 PRI me R 15. Polyethylene with associated antioxidant obtained using a titanium catalyst.

PRI me R 15A (polyethylene). Polyethylene can be produced using titanium catalysts. 900 ml of dehydrated hexane are charged into the Sutherland dispenser, purged several times to remove traces of oxygen, and pressure is raised to 0.31 MPa with ethylene. The reactor was heated ^to 40 ° C and to it was added 6.0 mmol of diethylaluminum chloride and 1.8 mmol of titanium trichloride beta. Ethylene is added continuously during the reaction to maintain the reaction pressure at 0.31 MPa. Twenty minutes after the start, 1.0 ml of isopropanol was added to stop the reaction. In order to remove residual solvent, the obtained polymer (17 g) is dried in an oven.

 PRI me R 15V (with bisphenol N). Polyethylene was prepared in the same manner as in Example 15A, except that another 0.096 g of bisphenol N was added. The obtained polymer (9.3 g) was reduced and reprecipitated before being examined by IR spectroscopy for the presence of bound phenolic groups. IR analysis showed that polyethylene contains bisphenol N in an amount of 0.33% by weight.

 PRI me R s 16-21. Investigation of the thermal aging of polymers containing bisphenol N.

 The following examples illustrate the thermal aging of EPM copolymers containing bisphenol N.

Samples of EPM and EPDM containing either admixed or copolymerized bisphenol N, was prepared and tested for resistance to thermal aging at ¹⁰⁰ ° C in an oven with forced air. Samples containing a mixed industrial manufactured antioxidant "Irganox 1076" company "Ciba-Geigy", and samples that do not contain antioxidant, are used as control. The compositions of the EPM samples are controlled by the viscosity of the reconstituted solution. EPDM compositions are controlled by gelation measurements. The results of thermal aging studies are listed in Tables 7 and 8.

CONTROL PRI me R 16A. The Sutherland dispenser is thoroughly flushed with nitrogen, after which the dispenser is filled, loading 900 ml of dehydrated hexane into it. After this dispenser again purged with nitrogen and propylene and pressurized to 0.31 MPa at ⁴⁰ ° C with a mixture which consists of 60% ethylene and 40% propylene. Then, ethyl aluminum sesquichloride (4.8 mmol), pyridine (0.3 mmol), butyl perchlorovinyl acetate (0.2 mmol) and vanadyl chloride (0.1 mmol) are added to the dispenser. The reaction is stopped after 20 minutes by adding 1.0 ml of isopropanol, and the polymer is isolated and dried. The reaction product is a copolymer of ethylene and propylene having a viscosity of the recovered solution of 1.9 and an ethylene content of 57 mol.

 CONTROL PRI me R 16V. The polymer obtained in Control Example 16A was dissolved in hexane. Bisphenol N (0.35 parts per 100 parts rubber) was added to the solution. Rubber is isolated by coagulation in acetone.

 CONTROL PRIMER 16C. The polymer obtained in Control Example 16A was dissolved in hexane. Bisphenol N (0.35 parts per 100 parts rubber) was added to the solution. Rubber is isolated by evaporation of hexane.

 CONTROL PRI me R 16D. The polymer obtained in Control Example 16A was dissolved in hexane. Irganox 1076 (0.35 parts per 100 parts rubber) was added to the solution. Rubber is isolated by evaporation of hexane.

 CONTROL PRI me R 17A. This polymer was prepared in the same manner as in Example 16 A, but an additional 1.0 g of ethylidene norbornene was added to the dispenser. The reaction product is an ethylene (propylene) ethylidene norbornene trimer having a solution recovery viscosity of 2.1, a molar ratio of ethylene and propylene of 65:35, and an ethylidene norbornene content of 4.6% by weight.

 CONTROL PRI me R 17V. The polymer obtained in Control Example 17A was dissolved in hexane. Bisphenol N (0.2 parts per 100 parts rubber) was added to the solution. Rubber is isolated by coagulation in acetone.

 CONTROL PRIMER 17C. The polymer obtained in Control Example 17A was dissolved in hexane. Biphenol N (0.2 parts per 100 parts rubber) is added to the solution. Rubber is isolated by evaporation of hexane.

 CONTROL PRI me R 17D. The polymer obtained in Control Example 17A was dissolved in hexane. Irganox 1076 (0.2 parts per 100 parts rubber) was added to the solution. Rubber is isolated by evaporation of hexane.

 EXAMPLES 17 and 18. These polymers are obtained in the same manner as in example 16, but bisphenol N is added as a solution of 0.6 g of bisphenol N in 25 ml of toluene. Various amounts of this solution are added to the reaction mixture to obtain a bisphenol N content of 0.2% by weight in Example 18 and 0.35% by weight in Example 19. The reaction products are trimers of ethylene (propylene) bisphenol N, their properties are listed in Table 7 along with the properties of the products obtained in Control Examples 16A D. Before the thermal aging test, the samples are dissolved in hexane and then coagulated with acetone.

 EXAMPLES 20 and 21. These polymers are obtained in the same manner as in example 17, but bisphenol N is added as a solution of bisphenol N in ethylene norbornene. In order to obtain a bisphenol N content of 0.1% by weight in Example 20 and 0.2% by weight in Example 21, different amounts of bisphenol N are added to the solution. In each example, an amount of ethylidene norbornene is added to the solution such that the total amount each time was 1.0 g. The reaction products are trimers of ethylene (propylene) bisphenol N, their properties are listed in Table 8 along with the properties of the products obtained in control examples 17 A-D. Before testing for thermal aging, the samples are dissolved in hexane, and then they are coagulated with acetone.

 Listed in the table. Figures 7 and 8 show that the polymerizable antioxidant bisphenol N in the form of a copolymer works in the same way as mixed antioxidants (comparison of bisphenol N copolymers with control samples C and D), and after 10 weeks it has the additional advantage of resistance to release or migration from the polymer (comparison of copolymers bisphenol N with controls A and B). A comparison of control samples A and B shows that coagulation in acetone removes the unbound antioxidant. The copolymerized bisphenol N is not removed by coagulation in acetone.

 PRI me R s 22-23. The influence of variable reactions on the implementation of bisphenol N.

 Bisphenol N does not manifest itself as a catalyst poison. This can be seen from the previous examples 4-8, where bisphenol N in an amount of 0.78-5.4% by weight, copolymerized in EPDM, had little effect on the amount of polymer produced. However, all these examples were carried out under similar conditions, so further experiments were performed to see if the same conclusions could be made at different levels of activator and / or at different levels of monomer concentrations.

 PRI me R s 22 A-D. The polymers were prepared in the same manner as in Examples 16 and 17, with the exception that the levels of the butyl perchlorovinyl acetate activator (butyl-PCVA) were different. Large quantities of bisphenol N are also used at two different levels. The results are shown in table.9.

 The data show a slight decrease in the molarity of the catalyst at high levels of bisphenol N. Such a slight decrease in molarity can be overcome by increasing the activator concentration.

 PRI me R s 23 A-D.

 The polymers are prepared in the same manner as in Examples 18-19, except that 0.6 mmol of butyl perchlorovinyl acetate activator is used, and the dispenser is fed with a mixture of 80% ethylene and 20% propylene. In order to regulate the molecular weight, hydrogen recharge is also carried out, maintaining its pressure at ordinary levels. The results are shown in table 10.

 The effect of hydrogen seems to be typical of a catalysis system in which the amount of bisphenol N is negligible. A slight effect of hydrogen on the chemical properties of polymers is also observed, as shown by measurements of VVR and permeation gel chromatography. The results are shown in table.11.

 PRI me R 24. Continuous polymerization with bisphenol N.

Reactions are carried out in a glass reactor with a capacity of 4 l, in the upper steel cover of which openings are made to add the necessary components, the cover is equipped with an immersion tube to remove liquid during polymerization, a mixer blade for mixing and an internal coil for cooling. The continuous polymerization is carried out at a temperature of 33 ^{° C} and a pressure of 0.33 MPa, temperature control is performed by circulating cold water through the cooling coil and pressure controlled by the amount of added catalyst. Hexane, monomers and other components are continuously added to the reactor during the entire time that a continuous stream of liquid flows from the reactor during polymerization so that the level of this liquid in the reactor is constant.

The reactor feed rates are: hexane 4.72 l / h, propylene -3.2 standard liters per minute, ethylene 1.90 standard liters per minute, hydrogen 17 cm ³ / min (93.5 mol. In terms of) and ammonia 1 12 cm ³ / min (0.50 mmol / L). Diluted solutions of ethyl aluminum sesquichloride, vanadium oxytrichloride and butyl perchlorocrotonate are added in separate streams at a feed rate of 10.0, 0.50 and 0.60 mmol / h, respectively. Ethylidene norbornene is added at a feed rate of 11.2 g / h dissolved in hexane. Bisphenol N is fed at a rate of from zero (experiment A) to 3.2 g / h (experiment B) and 6.1 g / h (experiment C). Bisphenol N is added as a solution of bisphenol N in ethylidene norbornene (EN).

A continuous stream of air ventilation (air flow rate of 450 cm ³ / min) is removed from the evaporation reactor to provide samples for gas chromatography and to prevent the inert gas from entering the reactor.

The polymer solution is unloaded from the reactor with continuous deactivation and washing of the solution with water in a second container with a mixer. The polymer exit rate after such a polymerization procedure is 200 g / h. Recovery of the polymer from the solution is carried out by steam stripping and the obtained polymer was dehydrated with hot air in an oven at 50-60 ^{° C} for 40 min. The "Irganox 1076" antioxidant is added in test A as a solution to the washed reactor before steam stripping. In experiments B and C, the addition of "Irganox 1076" is not produced. The results are shown in table 12.

 PRI me R 25. Polymerization of EPDM with alpha- (2,6-di-tri-butylphenol) -5-methylene-2-norbornene.

 Using the same general procedure as described in Example 9B, alpha- (2,6-di-tri-butylphenol) -5-methylene-2-norbornene is copolymerized with ethylene and propylene. The resulting polymer may contain a polymerizable antioxidant in an amount of 0.84% by weight.

 The amounts of antioxidant for each example are given in table.13.

 Thus, these data clearly show the amount of antioxidant introduced into the process and chemically bound to the (co) polymer.

Claims (7)

1. Spatially hindered phenols with antioxidant properties, formulas

where n 0 3;
R ₁ and R _{2 the} following substituents
R _{3 is} hydrogen or lower alkyl; or
A (R ₁ R ₂ ),
where R ₁ and R _{2 are} spatially hindered substituents, wherein R ₁ has the general formula

R ₂ R ₁ or has the formula

where X and X ¹ divalent oxygen;
R ₄ , R ₅ , R ₆ and R ₇ C ₁ C ₈ -alkyl;
R ₄ and R _{6 are} hydrogen;
R _{8 is} hydrogen or methyl or ethyl, the same or different. 2. The compound according to claim 1, characterized in that R ₄ , R ₅ , R ₆ and R ₇ are selected from the group: methyl, isopropyl or tert-butyl. 3. The compound according to claims 1 and 2, characterized in that X and X ¹ each oxygen. 4. The compound according to claims 1 to 3, characterized in that R ₁ and R ₂ are each group of the formula

5. The compound according to PP.1 to 5, characterized in that R ₃ hydrogen, R ₁ and R ₂ have the formula

and connected to the norbornene skeleton in o- or p-positions to the phenolic group. 6. A method of obtaining spatially hindered phenols with antioxidant properties, of the General formula

where n = 0 3;
R ₁ and R _{2 are} spatially hindered substituents, wherein R ₁ has the general formula

R ₂ = R ₁ or has the general formula

where R _{3 is} hydrogen or lower alkyl;
X and X ¹ divalent oxygen;
R ₄ , R ₅ , R ₆ and R _{7 are} each C ₁ -C ₈ alkyl;
R ₄ and R _{6 are} hydrogen;
R _{8 is} hydrogen, or methyl, or ethyl, the same or different,
characterized in that the interaction between the disubstituted phenol and the 2-norbornenocarboxylic acid is carried out during base catalysis in a lower alcohol medium as a solvent. 7. A method for producing spatially hindered phenols having antioxidant properties, of the general formula

where R ₁ has the General formula

R ₂ = R ₁ or has the general formula

X and X ¹ divalent oxygen;
R ₄ , R ₅ , R ₆ and R _{7 are} each C ₁ -C ₈ alkyl;
R ₄ and R _{6 are} hydrogen;
R _{8 is} hydrogen, or methyl, or ethyl, the same or different,
characterized in that the compound is obtained by the interaction between disubstituted phenol and β-or g-unsaturated norbornenone by catalysis with base in a lower alcohol medium as a solvent. 8. A method of producing polyolefins by polymerizing a-olefins or copolymerizing them with each other and / or with dienes in the presence of a Ziegler-type catalyst and a phenolic antioxidant, characterized in that spatially hindered bisphenol of the general formula is used as a phenolic antioxidant

where n = 0 3;
R ₁ and R _{2 the} following substituents;
R _{3 is} hydrogen or lower alkyl,
or A (R ₁ R ₂ ),
where R ₁ and R _{2 are} spatially hindered substituents, wherein R ₁ has the general formula

where R ₂ = R ₁ or has the General formula

X and X ¹ divalent oxygen;
R ₄ , R ₅ , R ₆ and R _{7 are} each C ₁ -C ₈ alkyl;
R ₄ and R _{6 are} hydrogen;
R _{8 is} hydrogen, or methyl, or ethyl, the same or different,
moreover, the process is carried out at a mass ratio of phenolic antioxidant: monomer (0.1 to 40) 100 and (co) polymerization is carried out to a content of phenolic antioxidant chemically bound to the (co) polymer, 0.05 to 20 wt. per 100 wt. (co) polymer. Priority on points:
07/10/90 according to paragraphs 1,2,3,4,5 and 7;
11/02/90 according to paragraphs 6 and 8.

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